PREPARATION METHOD OF CATALYST WITH WHITE CARBON BLACK MODIFIED BY Zr-Nd-O

ABSTRACT

The present invention discloses a preparation method of a catalyst with white carbon black modified by Zr—Nd—O and use thereof, and belongs to the field of catalyst technologies. In the present invention, an organic solvent evaporation induced self-assembly method is used to load Zr—Nd—O onto white carbon black to obtain a mesoporous Zr—Nd—O/white carbon black catalyst. The mesoporous Zr—Nd—O/white carbon black catalyst in the present invention has high catalytic activity, contains uniformly distributed mesopores with a relatively large average aperture, and has a simple preparation process, etc.

TECHNICAL FIELD

The present invention relates to a preparation method of a catalyst withwhite carbon black modified by Zr—Nd—O, and belongs to the field ofcatalyst technologies.

BACKGROUND

Acetylene gas, as a raw material used in the petrochemical industry, isused to prepare polyvinyl chloride (PVC), polybutadiene rubber, aceticacid, vinyl acetate, etc. As the PVC industry in China rapidly develops,there is an increasing demand for acetylene gas. At present, there aremainly two processes for production of acetylene gas: a wet process anda dry process. Compared with the dry process, the application of the wetprocess for production of acetylene gas is more common; however, the wetprocess has disadvantages of high water consumption, lower acetyleneyield, and large production of carbide slag slurry, and is easy to causegroundwater and soil pollution. The dry production process caneffectively overcome the disadvantages of the wet production process,and has obvious advantages in safety, economy, environmental protection,etc. Regardless of whether the dry process or the wet process isadopted, in addition to acetylene, crude acetylene also contains variousimpurity gas including hydrogen sulfide (H₂S), hydrogen phosphide (PH₃),arsenic hydride (AsH₃), ammonia gas (NH₃), and trace organic substances.Gas accounting for a larger content ratio in the impurity gas includeshydrogen sulfide and hydrogen phosphide gas. If not treated, the gaswill cause catalyst poisoning in production of polyvinyl chloride, andalso directly affect a yield of polyvinyl chloride. Moreover, the gaswill pose a threat to the surrounding environment and people's physicaland mental health. Therefore, it is quite necessary to purify crudeacetylene gas. At present, there are mainly two methods for removal ofhydrogen sulfide and hydrogen phosphide in acetylene gas: a wet processand a dry process. The wet process is widely used in purification ofcrude acetylene gas because of its advantages such as low price and easyoperation and management. In the wet process, a large amount ofwastewater is produced, which poses a threat to the environment. The dryprocess can effectively avoid wastewater production. However, atpresent, the dry process has relatively low impurity removal efficiency,and there is no efficient catalyst for simultaneously removing PH₃ andAsH₃.

SUMMARY

In view of a technical problem in the prior art that there is nocatalyst for simultaneously removing PH₃ and AsH₃, the present inventionprovides a preparation method of a catalyst with white carbon blackmodified by Zr—Nd—O and use thereof. The present invention uses anorganic solvent evaporation induced self-assembly method to load Zr—Nd—Oonto white carbon black to obtain a Zr—Nd—O/white carbon black catalyst.The Zr—Nd—O/white carbon black catalyst in the present invention hashigh catalytic activity, contains uniformly distributed mesopores with arelatively large average aperture, and has a simple preparation process,etc.

A preparation method of a catalyst with white carbon black modified byZr—Nd—O is provided, including the following specific steps:

(1) adding sodium chloride and ethanol to sodium silicate, uniformlymixing, and slowly adding water under stirring until sodium silicatecolloidal particles are dissolved, to obtain an ethanol-sodium silicatesolution mixture;

(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 25-45° C. under stirring to adjust a pH value of thesystem to 7.5-9.5; and conducting aging at 70-110° C. for 10-20 h toobtain white carbon black;

(3) adding the white carbon black in step (2) to ethanol under stirring,adding zirconium nitrate, neodymium nitrate, and a surfactant, andconducting reaction for 5-10 h to obtain a mixed white carbon blacksolution;

(4) evaporating ethanol from the mixed white carbon black solution instep (3) at 50-70° C. to obtain a precursor; and

(5) calcining the precursor in step (4) at 300-500° for 2-4 h to obtaina mesoporous Zr—Nd—O/white carbon black catalyst.

A solid-to-liquid ratio g:mL of the sodium chloride to the sodiumsilicate in step (1) is 1:(10-15), and a volume ratio of the ethanol tothe sodium silicate is 1:(0.8-1.2).

The surfactant in step (3) is a triblock copolymer P123, F127, or F108.In step (3), a mass ratio of the zirconium nitrate to the white carbonblack is 1:(1-2); a mass ratio of the neodymium nitrate to the whitecarbon black is 1:(3.3-6.7); and a mass ratio of the surfactant to thewhite carbon black is 1:(1-2).

The present invention provides use of a mesoporous Zr—Nd—O/white carbonblack catalyst prepared by using the preparation method of a catalystwith white carbon black modified by Zr—Nd—O in simultaneously removingPH₃ and AsH₃ through catalysis.

According to the use of the preparation method in the present invention,the surfactant is removed though calcination, so that the catalyst has amesoporous structure.

Beneficial effects of the present invention are as follows:

(1) In the present invention, an organic solvent evaporation inducedself-assembly method is used to load Zr—Nd—O onto white carbon black toobtain a Zr—Nd—O/white carbon black catalyst. The Zr—Nd—O/white carbonblack catalyst in the present invention has high catalytic activity,contains uniformly distributed mesopores with a relatively large averageaperture, and has a simple preparation process, etc.

(2) In the present invention, Zr—Nd—O/white carbon black catalysts withdifferent mesopore sizes can be obtained by using different surfactants.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an effect diagram of simultaneously removing PH₃ and AsH₃ byusing a mesoporous Zr—Nd—O/white carbon black catalyst according toEmbodiment 1;

FIG. 2 is an effect diagram of simultaneously removing PH₃ and AsH₃ byusing a mesoporous Zr—Nd—O/white carbon black catalyst according toEmbodiment 2;

FIG. 3 is an effect diagram of simultaneously removing PH₃ and AsH₃ byusing a mesoporous Zr—Nd—O/white carbon black catalyst according toEmbodiment 3;

FIG. 4 is an effect diagram of simultaneously removing PH₃ and AsH₃ byusing a mesoporous Zr—Nd—O/white carbon black catalyst according toEmbodiment 4;

FIG. 5 is an effect diagram of simultaneously removing PH₃ and AsH₃ byusing a mesoporous Zr—Nd—O/white carbon black catalyst according toEmbodiment 5;

FIG. 6 is an effect diagram of simultaneously removing PH₃ and AsH₃ byusing a mesoporous Zr—Nd—O/white carbon black catalyst according toEmbodiment 6;

FIG. 7 is an effect diagram of simultaneously removing PH₃ and AsH₃ byusing a mesoporous Zr—Nd—O/white carbon black catalyst according toEmbodiment 7;

FIG. 8 is an effect diagram of simultaneously removing PH₃ and AsH₃ byusing a mesoporous Zr—Nd—O/white carbon black catalyst according toEmbodiment 8; and

FIG. 9 is an effect diagram of simultaneously removing PH₃ and AsH₃ byusing a mesoporous Zr—Nd—O/white carbon black catalyst according toEmbodiment 9.

DETAILED DESCRIPTION

The present invention will be further described in details below withreference to specific implementations, but the protection scope of thepresent invention is not limited thereto.

Embodiment 1: a preparation method of a catalyst with white carbon blackmodified by Zr—Nd—O is provided, including the following specific steps:

(1) adding sodium chloride and ethanol to sodium silicate, uniformlymixing, and slowly adding water under stirring until sodium silicatecolloidal particles are dissolved, to obtain an ethanol-sodium silicatesolution mixture, where a solid-to-liquid ratio g:mL of the sodiumchloride to the sodium silicate is 1:10, and a volume ratio of theethanol to the sodium silicate is 1:0.8;

(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 40° C. under stirring to adjust a pH value of the systemto 8.0; and conducting aging at 90° C. for 15 h to obtain white carbonblack;

(3) adding the white carbon black in step (2) to ethanol under stirring,adding zirconium nitrate, neodymium nitrate, and a surfactant (P123),and conducting reaction for 8 h to obtain a mixed white carbon blacksolution, where a mass ratio of the zirconium nitrate to the whitecarbon black is 1:1; a mass ratio of the neodymium nitrate to the whitecarbon black is 1:3.3; and a mass ratio of the surfactant (P123) to thewhite carbon black is 1:1;

(4) evaporating ethanol from the mixed white carbon black solution instep (3) at 65° C. to obtain a precursor; and

(5) calcining the precursor in step (4) at 450° for 2.5 h to obtain amesoporous Zr—Nd—O/white carbon black catalyst.

The catalytic performance test of the mesoporous Zr—Nd—O/white carbonblack catalyst in this embodiment is conducted in a 16 mm×10 cm quartzfixed bed reactor. Reaction conditions are as follows: An initialconcentration of PH₃ is 200 ppm, an initial concentration of AsH₃ is 100ppm, equilibrium gas is C₂H₂, a space velocity is 15000 and the reactiontemperature is 70° C. A test result is shown in FIG. 1. It can be seenfrom FIG. 1 that the catalyst has a better removal effect on AsH₃ thanPH₃ in a removal stage corresponding to the removal efficiency 100%.However, as removal time increases, the catalyst has a better removaleffect on PH₃ than AsH₃.

Embodiment 2: a preparation method of a catalyst with white carbon blackmodified by Zr—Nd—O is provided, including the following specific steps:

(1) adding sodium chloride and ethanol to sodium silicate, uniformlymixing, and slowly adding water under stirring until sodium silicatecolloidal particles are dissolved, to obtain an ethanol-sodium silicatesolution mixture, where a solid-to-liquid ratio g:mL of the sodiumchloride to the sodium silicate is 1:12.5, and a volume ratio of theethanol to the sodium silicate is 1:1;

(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 40° C. under stirring to adjust a pH value of the systemto 8.0; and conducting aging at 90° C. for 15 h to obtain white carbonblack;

(3) adding the white carbon black in step (2) to ethanol under stirring,adding zirconium nitrate, neodymium nitrate, and a surfactant (P123),and conducting reaction for 8 h to obtain a mixed white carbon blacksolution, where a mass ratio of the zirconium nitrate to the whitecarbon black is 1:1.5; a mass ratio of the neodymium nitrate to thewhite carbon black is 1:5; and a mass ratio of the surfactant (P123) tothe white carbon black is 1:1.5;

(4) evaporating ethanol from the mixed white carbon black solution instep (3) at 65° C. to obtain a precursor; and

(5) calcining the precursor in step (4) at 450° for 2.5 h to obtain amesoporous Zr—Nd—O/white carbon black catalyst.

The catalytic performance test of the mesoporous Zr—Nd—O/white carbonblack catalyst in this embodiment is conducted in a 16 mm×10 cm quartzfixed bed reactor. Reaction conditions are as follows: An initialconcentration of PH₃ is 200 ppm, an initial concentration of AsH₃ is 100ppm, equilibrium gas is C₂H₂, a space velocity is 15000 and the reactiontemperature is 70° C. A test result is shown in FIG. 2. It can be seenfrom FIG. 2 that the AsH₃ removal efficiency 100% of the catalyst can bemaintained for 420 min, and the catalyst has a better removal effect onAsH₃ than PH₃ in the whole removal process.

Embodiment 3: a preparation method of a catalyst with white carbon blackmodified by Zr—Nd—O is provided, including the following specific steps:

(1) adding sodium chloride and ethanol to sodium silicate, uniformlymixing, and slowly adding water under stirring until sodium silicatecolloidal particles are dissolved, to obtain an ethanol-sodium silicatesolution mixture, where a solid-to-liquid ratio g:mL of the sodiumchloride to the sodium silicate is 1:15, and a volume ratio of theethanol to the sodium silicate is 1:1.2;

(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 40° C. under stirring to adjust a pH value of the systemto 8.0; and conducting aging at 90° C. for 15 h to obtain white carbonblack;

(3) adding the white carbon black in step (2) to ethanol under stirring,adding zirconium nitrate, neodymium nitrate, and a surfactant (P123),and conducting reaction for 8 h to obtain a mixed white carbon blacksolution, where a mass ratio of the zirconium nitrate to the whitecarbon black is 1:2; a mass ratio of the neodymium nitrate to the whitecarbon black is 1:6.7; and a mass ratio of the surfactant (P123) to thewhite carbon black is 1:2;

(4) evaporating ethanol from the mixed white carbon black solution instep (3) at 65° C. to obtain a precursor; and

(5) calcining the precursor in step (4) at 450° for 2.5 h to obtain amesoporous Zr—Nd—O/white carbon black catalyst.

The catalytic performance test of the mesoporous Zr—Nd—O/white carbonblack catalyst in this embodiment is conducted in a 16 mm×10 cm quartzfixed bed reactor. Reaction conditions are as follows: An initialconcentration of PH₃ is 200 ppm, an initial concentration of AsH₃ is 100ppm, equilibrium gas is C₂H₂, a space velocity is 15000 and the reactiontemperature is 70° C. A test result is shown in FIG. 3. It can be seenfrom FIG. 3 that the catalyst has a relatively good removal effect onboth AsH₃ and PH₃.

Embodiment 4: a preparation method of a catalyst with white carbon blackmodified by Zr—Nd—O is provided, including the following specific steps:

(1) adding sodium chloride and ethanol to sodium silicate, uniformlymixing, and slowly adding water under stirring until sodium silicatecolloidal particles are dissolved, to obtain an ethanol-sodium silicatesolution mixture, where a solid-to-liquid ratio g:mL of the sodiumchloride to the sodium silicate is 1:10, and a volume ratio of theethanol to the sodium silicate is 1:0.8;

(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 40° C. under stirring to adjust a pH value of the systemto 8.0; and conducting aging at 90° C. for 15 h to obtain white carbonblack;

(3) adding the white carbon black in step (2) to ethanol under stirring,adding zirconium nitrate, neodymium nitrate, and a surfactant (F127),and conducting reaction for 8 h to obtain a mixed white carbon blacksolution, where a mass ratio of the zirconium nitrate to the whitecarbon black is 1:1; a mass ratio of the neodymium nitrate to the whitecarbon black is 1:3.3; and a mass ratio of the surfactant (F127) to thewhite carbon black is 1:1;

(4) evaporating ethanol from the mixed white carbon black solution instep (3) at 65° C. to obtain a precursor; and

(5) calcining the precursor in step (4) at 450° for 2.5 h to obtain amesoporous Zr—Nd—O/white carbon black catalyst.

The catalytic performance test of the mesoporous Zr—Nd—O/white carbonblack catalyst in this embodiment is conducted in a Φ6 mm×10 cm quartzfixed bed reactor. Reaction conditions are as follows: An initialconcentration of PH₃ is 200 ppm, an initial concentration of AsH₃ is 100ppm, equilibrium gas is C₂H₂, a space velocity is 15000 and the reactiontemperature is 70° C. A test result is shown in FIG. 4. It can be seenfrom FIG. 4 that a PH₃ removal effect and an AsH₃ removal effect of thecatalyst are basically consistent during a removal time of 360 min; andthe catalyst has higher PH₃ removal efficiency than the AsH₃ removalefficiency after the removal time of 360 min.

Embodiment 5: a preparation method of a catalyst with white carbon blackmodified by Zr—Nd—O is provided, including the following specific steps:

(1) adding sodium chloride and ethanol to sodium silicate, uniformlymixing, and slowly adding water under stirring until sodium silicatecolloidal particles are dissolved, to obtain an ethanol-sodium silicatesolution mixture, where a solid-to-liquid ratio g:mL of the sodiumchloride to the sodium silicate is 1:12.5, and a volume ratio of theethanol to the sodium silicate is 1:1;

(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 40° C. under stirring to adjust a pH value of the systemto 8.0; and conducting aging at 90° C. for 15 h to obtain white carbonblack;

(3) adding the white carbon black in step (2) to ethanol under stirring,adding zirconium nitrate, neodymium nitrate, and a surfactant (F127),and conducting reaction for 8 h to obtain a mixed white carbon blacksolution, where a mass ratio of the zirconium nitrate to the whitecarbon black is 1:1.5; a mass ratio of the neodymium nitrate to thewhite carbon black is 1:5; and a mass ratio of the surfactant (F127) tothe white carbon black is 1:1.5;

(4) evaporating ethanol from the mixed white carbon black solution instep (3) at 65° C. to obtain a precursor; and

(5) calcining the precursor in step (4) at 450° for 2.5 h to obtain amesoporous Zr—Nd—O/white carbon black catalyst.

The catalytic performance test of the mesoporous Zr—Nd—O/white carbonblack catalyst in this embodiment is conducted in a Φ6 mm×10 cm quartzfixed bed reactor. Reaction conditions are as follows: An initialconcentration of PH₃ is 200 ppm, an initial concentration of AsH₃ is 100ppm, equilibrium gas is C₂H₂, a space velocity is 15000 and the reactiontemperature is 70° C. A test result is shown in FIG. 5. It can be seenfrom FIG. 5 that the catalyst has a better removal effect on PH₃ thanAsH₃ during a removal time of 300 min; and the PH₃ removal efficiencyand the AsH₃ removal efficiency of the catalyst are basically consistentafter 300 min.

Embodiment 6: a preparation method of a catalyst with white carbon blackmodified by Zr—Nd—O is provided, including the following specific steps:

(1) adding sodium chloride and ethanol to sodium silicate, uniformlymixing, and slowly adding water under stirring until sodium silicatecolloidal particles are dissolved, to obtain an ethanol-sodium silicatesolution mixture, where a solid-to-liquid ratio g:mL of the sodiumchloride to the sodium silicate is 1:15, and a volume ratio of theethanol to the sodium silicate is 1:1.2;

(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 40° C. under stirring to adjust a pH value of the systemto 8.0; and conducting aging at 90° C. for 15 h to obtain white carbonblack;

(3) adding the white carbon black in step (2) to ethanol under stirring,adding zirconium nitrate, neodymium nitrate, and a surfactant (F127),and conducting reaction for 8 h to obtain a mixed white carbon blacksolution, where a mass ratio of the zirconium nitrate to the whitecarbon black is 1:2; a mass ratio of the neodymium nitrate to the whitecarbon black is 1:6.7; and a mass ratio of the surfactant (F127) to thewhite carbon black is 1:2;

(4) evaporating ethanol from the mixed white carbon black solution instep (3) at 65° C. to obtain a precursor; and

(5) calcining the precursor in step (4) at 450° for 2.5 h to obtain amesoporous Zr—Nd—O/white carbon black catalyst.

The catalytic performance test of the mesoporous Zr—Nd—O/white carbonblack catalyst in this embodiment is conducted in a 16 mm×10 cm quartzfixed bed reactor. Reaction conditions are as follows: An initialconcentration of PH₃ is 200 ppm, an initial concentration of AsH₃ is 100ppm, equilibrium gas is C₂H₂, a space velocity is 15000 and the reactiontemperature is 70° C. A test result is shown in FIG. 6. It can be seenfrom FIG. 6 that, the PH₃ removal efficiency 100% and the AsH₃ removalefficiency 100% of the catalyst can be maintained for 120 min, and thewhole PH₃ removal efficiency and the whole AsH₃ removal efficiency ofthe catalyst are basically consistent.

Embodiment 7: a preparation method of a catalyst with white carbon blackmodified by Zr—Nd—O is provided, including the following specific steps:

(1) adding sodium chloride and ethanol to sodium silicate, uniformlymixing, and slowly adding water under stirring until sodium silicatecolloidal particles are dissolved, to obtain an ethanol-sodium silicatesolution mixture, where a solid-to-liquid ratio g:mL of the sodiumchloride to the sodium silicate is 1:10, and a volume ratio of theethanol to the sodium silicate is 1:0.8;

(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 40° C. under stirring to adjust a pH value of the systemto 8.0; and conducting aging at 90° C. for 15 h to obtain white carbonblack;

(3) adding the white carbon black in step (2) to ethanol under stirring,adding zirconium nitrate, neodymium nitrate, and a surfactant (F108),and conducting reaction for 8 h to obtain a mixed white carbon blacksolution, where a mass ratio of the zirconium nitrate to the whitecarbon black is 1:1; a mass ratio of the neodymium nitrate to the whitecarbon black is 1:3.3; and a mass ratio of the surfactant (F108) to thewhite carbon black is 1:1;

(4) evaporating ethanol from the mixed white carbon black solution instep (3) at 65° C. to obtain a precursor; and

(5) calcining the precursor in step (4) at 450° for 2.5 h to obtain amesoporous Zr—Nd—O/white carbon black catalyst.

The catalytic performance test of the mesoporous Zr—Nd—O/white carbonblack catalyst in this embodiment is conducted in a 16 mm×10 cm quartzfixed bed reactor. Reaction conditions are as follows: An initialconcentration of PH₃ is 200 ppm, an initial concentration of AsH₃ is 100ppm, equilibrium gas is C₂H₂, a space velocity is 15000 and the reactiontemperature is 70° C. A test result is shown in FIG. 7. It can be seenfrom FIG. 7 that, the PH₃ removal efficiency of the catalyst is 100%before 250 min, and the whole PH₃ removal efficiency of the catalyst isobviously higher than its PH₃ removal efficiency.

Embodiment 8: a preparation method of a catalyst with white carbon blackmodified by Zr—Nd—O is provided, including the following specific steps:

(1) adding sodium chloride and ethanol to sodium silicate, uniformlymixing, and slowly adding water under stirring until sodium silicatecolloidal particles are dissolved, to obtain an ethanol-sodium silicatesolution mixture, where a solid-to-liquid ratio g:mL of the sodiumchloride to the sodium silicate is 1:12.5, and a volume ratio of theethanol to the sodium silicate is 1:1;

(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 40° C. under stirring to adjust a pH value of the systemto 8.0; and conducting aging at 90° C. for 15 h to obtain white carbonblack;

(3) adding the white carbon black in step (2) to ethanol under stirring,adding zirconium nitrate, neodymium nitrate, and a surfactant (F108),and conducting reaction for 8 h to obtain a mixed white carbon blacksolution, where a mass ratio of the zirconium nitrate to the whitecarbon black is 1:1.5; a mass ratio of the neodymium nitrate to thewhite carbon black is 1:5; and a mass ratio of the surfactant (F108) tothe white carbon black is 1:1.5;

(4) evaporating ethanol from the mixed white carbon black solution instep (3) at 65° C. to obtain a precursor; and

(5) calcining the precursor in step (4) at 450° for 2.5 h to obtain amesoporous Zr—Nd—O/white carbon black catalyst.

The catalytic performance test of the mesoporous Zr—Nd—O/white carbonblack catalyst in this embodiment is conducted in a 16 mm×10 cm quartzfixed bed reactor. Reaction conditions are as follows: An initialconcentration of PH₃ is 200 ppm, an initial concentration of AsH₃ is 100ppm, equilibrium gas is C₂H₂, a space velocity is 15000 and the reactiontemperature is 70° C. A test result is shown in FIG. 8. It can be seenfrom FIG. 8 that, the AsH₃ removal efficiency of the catalyst is 100%before 150 min, and the whole AsH₃ removal efficiency of the catalyst isobviously lower than its PH₃ removal efficiency.

Embodiment 9: a preparation method of a catalyst with white carbon blackmodified by Zr—Nd—O is provided, including the following specific steps:

(1) adding sodium chloride and ethanol to sodium silicate, uniformlymixing, and slowly adding water under stirring until sodium silicatecolloidal particles are dissolved, to obtain an ethanol-sodium silicatesolution mixture, where a solid-to-liquid ratio g:mL of the sodiumchloride to the sodium silicate is 1:15, and a volume ratio of theethanol to the sodium silicate is 1:1.2;

(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 40° C. under stirring to adjust a pH value of the systemto 8.0; and conducting aging at 90° C. for 15 h to obtain white carbonblack;

(3) adding the white carbon black in step (2) to ethanol under stirring,adding zirconium nitrate, neodymium nitrate, and a surfactant (F108),and conducting reaction for 8 h to obtain a mixed white carbon blacksolution, where a mass ratio of the zirconium nitrate to the whitecarbon black is 1:2; a mass ratio of the neodymium nitrate to the whitecarbon black is 1:6.7; and a mass ratio of the surfactant (F108) to thewhite carbon black is 1:2;

(4) evaporating ethanol from the mixed white carbon black solution instep (3) at 65° C. to obtain a precursor; and

(5) calcining the precursor in step (4) at 450° for 2.5 h to obtain amesoporous Zr—Nd—O/white carbon black catalyst.

The catalytic performance test of the mesoporous Zr—Nd—O/white carbonblack catalyst in this embodiment is conducted in a 16 mm×10 cm quartzfixed bed reactor. Reaction conditions are as follows: An initialconcentration of PH₃ is 200 ppm, an initial concentration of AsH₃ is 100ppm, equilibrium gas is C₂H₂, a space velocity is 15000 h⁻¹, and thereaction temperature is 70° C. A test result is shown in FIG. 9. It canbe seen from FIG. 3 that, after 200 min, the AsH₃ removal efficiency ofthe catalyst is still lower than its PH₃ removal efficiency, but thewhole AsH₃ removal efficiency is obviously improved compared with thatin Embodiment 8.

1. A preparation method of a catalyst with white carbon black modifiedby Zr—Nd—O, comprising the following specific steps: (1) adding sodiumchloride and ethanol to sodium silicate, uniformly mixing, and slowlyadding water under stirring until sodium silicate colloidal particlesare dissolved, to obtain an ethanol-sodium silicate solution mixture;(2) adding sulfuric acid to the ethanol-sodium silicate solution mixturein step (1) at 25-45° C. under stirring to adjust a pH value of thesystem to 7.5-9.5; and conducting aging at 70-110° C. for 10-20 h toobtain white carbon black; (3) adding the white carbon black in step (2)to ethanol under stirring, adding zirconium nitrate, neodymium nitrate,and a surfactant, and conducting reaction for 5-10 h to obtain a mixedwhite carbon black solution; (4) evaporating ethanol from the mixedwhite carbon black solution in step (3) at 50-70° C. to obtain aprecursor; and (5) calcining the precursor in step (4) at 300-500° for2-4 h to obtain a mesoporous Zr—Nd—O/white carbon black catalyst.
 2. Thepreparation method according to claim 1, wherein a solid-to-liquid ratiog:mL of the sodium chloride to the sodium silicate in step (1) is1:(10-15), and a volume ratio of the ethanol to the sodium silicate is1:(0.8-1.2).
 3. The preparation method according to claim 1, wherein thesurfactant in step (3) is a triblock copolymer P123, F127, or F108. 4.The preparation method according to claim 1, wherein in step (3), a massratio of the zirconium nitrate to the white carbon black is 1:(1-2); amass ratio of the neodymium nitrate to the white carbon black is1:(3.3-6.7); and a mass ratio of the surfactant to the white carbonblack is 1:(1-2).
 5. Use of a mesoporous Zr—Nd—O/white carbon blackcatalyst prepared by using the preparation method of a catalyst withwhite carbon black modified by Zr—Nd—O according to claim 1 insimultaneously removing PH₃ and AsH₃ through catalysis.
 6. Use of amesoporous Zr—Nd—O/white carbon black catalyst prepared by using thepreparation method of a catalyst with white carbon black modified byZr—Nd—O according to claim 2 in simultaneously removing PH₃ and AsH₃through catalysis.
 7. Use of a mesoporous Zr—Nd—O/white carbon blackcatalyst prepared by using the preparation method of a catalyst withwhite carbon black modified by Zr—Nd—O according to claim 3 insimultaneously removing PH₃ and AsH₃ through catalysis.
 8. Use of amesoporous Zr—Nd—O/white carbon black catalyst prepared by using thepreparation method of a catalyst with white carbon black modified byZr—Nd—O according to claim 4 in simultaneously removing PH₃ and AsH₃through catalysis.